N-carboxyacyl- and n-carboxyaroylcarboxy piperidines



United States Patent O we Famed fffiii The mixture is heated to a temperature of about 200 3,335,145 0. During the heating period, methanol is liberated. The

N'CARBOXE liberated methanol is condensed and collected in a gradu- Francis E. Cisiak and Frank A. Karnatz, indianapolis, ated cylinder f about 40 of methanffl has been Ind assigmrs to m & Chemical Corporation, 5 collected, the heating 1S stopped, and the reaction mixture Indianapolis, ind, a corporation of Indiana is cooled. The N-adipyl-dinipecotic acid formed during No Drawing. Filed Jan. 25, 1965, Ser. No. 427,913 the heating period is a semi-refined product pure enough 6 Claims- (Cl- 26029 for most uses. If, however, a purer material is desired,

the semi-refined product may be purified further by extrac- Th1s application is a COHtlI'lllElllOIl-lH-PQIT of Ser. No. 10 tion with ether 9 filed M 1963' and now q P The N-adipyl-dinipecotic acid is soluble in water, meth- Th1s 1nvent1on relates to new compositions of matter anol and ethylene glycol. It is insoluble in benzene and and to the process of making them. More particularly, it hexane relates to N-carb015Wcykcarboxypiperidines and Our N-adipyl-dinipecotic acid is useful in the preparalfnoxyaioyl-carboxypiperldines which compounds have the tion of cross linked polyester resins mm a R1 EXAMPLE 2 N-adz'pyl-isonipecotic acid R2 s COOH CODE N/ O=-ACOOH S wherein R represents hydrogen, lower alkyl group (i.e., N an alkyl group of from 1 to 5 carbon atoms) or a car- 1] boxyl group, R represents hydrogen orlower alkyl, and A O=C*(CH) 4-0001; represents an alkylene group (such as (CH wherein A mixture of 129 grams of isonipecotic acid, 146 grams n is a Whole number from 1 to 11), lower alkenylene of adipic acid, and 400 cc. diethylbenzene is placed into (such as a one-liter flask. The flask is connected to a reflux con- CH=CH-, CH3C=CH- denser and a Dean-Stark water trap. The mixture is heated under reflux conditions (about 180 C.) and the CH2=CCH2) water formed by the interaction of the adipic acid and the l isonipecotic acid is collected in the Water trap. When p y about 18.0 cc. of water has been collected in the trap, the

our N-carboxyacyl-cg'lrboxypiperidinesfind our heating is stopped. The flask is allowed to cool, and the boxyaroyl'carboxyplpendmes are useful the manufac' diethylbenzene remaining Wtth the N-adipyl-isonipecotic ture of poly-esters by interaction with polyhydric alcohols acid, which was f d during the heating perioi Any f manufacture Polyamldes by the q g t 'diethylbenzene remaining With the N-adipyl-isonipecotic w th d1am1nes. The reaction of our new carboxypiperidmes acid is evaporated under vacuum. The hot, molten 1- Wlth monohydrlcfilcohols gives esters Whlch useful 40 isonipecotic acid is poured into a shallow pan and allowed plastlclzel's- The Zlnc, Copper, mercylry, and cadfmum Salts to cool. The N-adipyl-isonipecotic acid is soluble in Water, of 2 1 new compounds have fllllglcldal Properties and alcohols; it is insoluble in hydrocarbon solvents. use u in protection against mi ew, rot, etc.

In general our N-carboxyacyl-carboxypiperidines and EXAMPLE 3 our N-carboxyaroyl-carboxypiperidines may be prepared N-glzttalyl-nipectotic acid by heating a piperidine carboxylic acid with a mono-ester of a dibasic acid. The equation below depicts the prepara- COOH tion of N-adipyl isonipecotic acid by the interaction of s mono-methyl ester of adipic acid and isonipecotic acid: N

(IIOOH COOH o=( 3(cHi tooo1=r The procedure of Example 2 is repeated with the ex- S MEOOC (CH2) COOH A s ception that 132 grams of glutaric acid is used in place of the ad1p1c acid and 129 grams of mpecotic acid 15 used N f instead of the isonipectotic acid.

O=C(CHz)4-COOH EXAMPLE 4 The following specific examples illustrate the manner in which our invention may be practiced. These examples N 'phthaly l'isonipecofic acid are given by the way of illustration only and are not to COOH be construed as a limitation of our invention.

EXAMPLE 1 S N-adipyl-dinipecotic acid HO 0 c- -c 0 OH COOH To 180 grams of molten mono-methyl ester of phthalic O= (CH2)4 COOH acid in a one-liter flask there is added 129 grams of A mixture of 173 grams of dinipecotic acid and 160 isonipecotic acid. The flask containing the resulting mixgrams of methyl ester of adipic acid is placed in a oneture is connected to a condenser. The mixture is gradualliter flask. The flask is connected with a condenser. ly heated to a temperature of about 200 C. During the heating the methyl phthalate reacts with the isonipecotic acid, methanol being evolved. The methanol is condensed. When about 40 cc. of methanol is collected, the heating is stopped, and the reaction mixture is allowed to cool a bit and while the reaction product is still fluid, it is poured into a shallow pan and cooled.

EXAMPLE 5 N-terephthalyZ-isonipecotic acid C O OH The procedure of Example 4 is followed with the exception that the mono-methyl ester of terephthalic acid is used in place of the methylphthalate.

EXAMPLE 6 Maleic acid piperidide of isonipecotic acid COOH The procedure of Example 1 is repeated with the exception that 144 grams of the mono-ethyl ester of maleic. acid is used in place of the methyl adipate.

EXAMPLE 7 N-adipyl-pipecolinic acid (JOOH i O:C-- (CH2) 4CO OH The procedure of Example 2 is repeated save that pipecolinic acid is used in place .of the isonipecotic acid.

EXAMPLE 8 N-adipyl-S-methylnipecotic acid HAG 00011 The procedure of Example 2 is repeated save that 143 grams of S-methylnipecotic acid is used in place of the 129 grams of isonipecotic acid.

4 EXAMPLE 9 N-sebacyl-isonipecotic acid CooHv N O=( J-(GHz)a-COOH The procedure of Example 1 is repeated with the exception that 129 grams of isonipecotic acid is used in place of the dinipecoticacid and 216 grams of the methyl ester of sebacic acid is used in place of the methyl ester of adipic acid.

EXAMPLE l0 N-brassylyZ-isonipecotic acid C O O H r O=C'-(CH1)HCOOH The procedure of Example 1 is repeated with the exception that 129 grams of isonipecoticacid is used in place of the dinipecotic acid and 258 grams of the methyl ester of brassylic acid is used in place of the methyl ester of adipic acid.

We claim as our invention: 1. A compound of the formula References Cited FOREIGN PATENTS 855,115 11/1952 Germany.

WALTER A. MODANCE, Primary Examiner. A. D. SPEVACK, Assistant Examiner, 

1. A COMPOUND OF THE FORMULA 